The low‐temperature near‐band‐edge photoluminescence of thick (d≊36 &mgr;m) (100)CdTe epilayers grown on (100)GaAs substrates is investigated. Besides a dominating bound exciton emission, evidence for free‐exciton emission (n=1 and 2) and two electron transitions (TETs) of donor‐bound excitons is found. The defect involved in the TET is most likely a gallium‐related donor. This is concluded from the TET line wavelength adopting recent bulk CdTe TET data. A new emission line at 781.4 nm (1586.7 meV) is observed. It is tentatively assigned to a TET of a free exciton.